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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Sterically hindered electron-withdrawing ligands:the reactions of N-carbazolyl phosphines with rhodium and palladium centres
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Sterically hindered electron-withdrawing ligands:the reactions of N-carbazolyl phosphines with rhodium and palladium centres

机译：立体位阻吸电子配体：N-咔唑基膦与铑和钯中心的反应

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摘要

The series of N-carbazolyl phosphines PPH_(3-n)(NC_(12)H_8)_n(n = 1,L~1;n = 1,L_2;n-3,L~3)has been synthesised using BuLi to generate the N-carbazolyl lithium salt,followed by reaction with the appropriate chlorophosphine.The reactions between [Rh(mu-Cl)(CO)_2]_2 and four equivalents of L~1 or L_2 gave [RhCl(CO)(L~1)_2] 1 and [RhCl(CO)(L_2)_2] 2,though attempts to synthesise the analogous complex using L~3 resulted in the formation of [Rh(mu-Cl)(CO)(L~3)]_2 3 instead.The inability of L~3 to cleave the chloride bridges can be related to its considerable steric requirements.The electronic properties of L~1~3 were assessed by comparison of the v(CO)values of the [Rh(acac)(CO)(L~(1-3))] complexes 4-6.The increase in number of N-carbazolyl substituents at the phosphorus atom results in a decrease of the delta-donor and increase in the pi-acceptor character in the order L~1 < L_2 < L~3.In the reactions of L~(1-3)with [PdCl_2(cod)J only L~1 was able to displace cod from the metal centre and form [PdCl_2(L~1)_2] 7.The use of [PdCl_2(NCMe)_2] instead of [PdCl_2(cod)j resulted in the formation of the complexes [PdCl_2(L~1)_2] 7 from L~1,the cyclometallated complex [Pd(mu-Cl){P(NCl_2H_8)_2(NCl_2H_7)-Kappa~2.P,C}]_2 8 from L~3,and a mixture of [PdCl_2(L_2)_2] 9 and [Pd(mu-Cl){PPh(NCl_2H_8)(NCl_2H_7)-Kappa~2P,C}]_210 from L_2.The reaction of L~3 with [Pd(OAc)_2] produced the cyclometallated complex [Pd(mu-O_2CCH_3){P(NCl_2H_8)_2(NCl_2H_7)-Kappa~2P,C}]_211.The reaction of L~3 with [Pd_2(dba)_3]-CHCL~3 produced the 14-electron complex [Pd(L~3)_2] 12.The X-ray crystal structures of six complexes are reported,all of which show the presence of C-H...Pd hydrogen bonding.
机译：使用BuLi合成了一系列N-咔唑基膦PPH_（3-n）（NC_（12）H_8）_n（n = 1，L〜1; n = 1，L_2; n-3，L〜3）生成N-咔唑基锂盐，然后与适当的氯膦反应。[Rh（mu-Cl）（CO）_2] _2与四个当量的L〜1或L_2反应得到[RhCl（CO）（L〜 1）_2] 1和[RhCl（CO）（L_2）_2] 2，尽管尝试使用L〜3合成类似物导致形成[Rh（mu-Cl）（CO）（L〜3）] _2 3相反。L〜3无法裂解氯离子桥可能与其相当的空间要求有关。L〜1〜3的电子性质通过比较[Rh（acac）的v（CO）值进行评估）（CO）（L〜（1-3））]配合物4-6。磷原子上N-咔唑基取代基数目的增加导致δ-供体的减少和pi-受体特性的增加。在L〜（1-3）与[PdCl_2（cod）J]的反应中，只有L〜1能够从金属中心置换cod，而f orm [PdCl_2（L〜1）_2]7。使用[PdCl_2（NCMe）_2]代替[PdCl_2（cod）j]导致L〜形成配合物[PdCl_2（L〜1）_2] 7 1，来自L〜3的环金属化配合物[Pd（mu-Cl）{P（NCl_2H_8）_2（NCl_2H_7）-Kappa〜2.P，C}] _ 2 8和[PdCl_2（L_2）_2]的混合物9和来自L_2的[Pd（mu-Cl）{PPh（NCl_2H_8）（NCl_2H_7）-Kappa〜2P，C}] _210。L〜3与[Pd（OAc）_2]的反应生成环化金属配合物[Pd（mu -O_2CCH_3）{P（NCl_2H_8）_2（NCl_2H_7）-Kappa〜2P，C}] _211。L〜3与[Pd_2（dba）_3] -CHCL〜3的反应生成14电子配合物[Pd（L 〜3）_2] 12.报道了六个配合物的X射线晶体结构，所有这些均显示存在CH ... Pd氢键。

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